Use of amines and/or Mannich adducts in fuel and lubricant compositions for direct injection spark ignition engines

ABSTRACT

The present invention relates to the use of amines and/or Mannich adducts as detergents and/or dispersants in fuel and lubricant compositions for direct-injection gasoline engines. The invention further relates to fuel and lubricant compositions which comprise at least one such Mannich adduct, and also a bisaminoalkylated Mannich adduct.

This application is a continuation of Ser. No. 10/536,401 which is theUS national phase of international application PCT/EP2003/013512 filed 1Dec. 2003 which designated the U.S. and claims benefit of DE 102 56161.3, dated 2 Dec. 2002, the entire contents of which is herebyincorporated by reference.

The present invention relates to the use of amines and/or Mannichadducts as detergents and/or dispersants in fuel and lubricantcompositions for direct-injection gasoline engines. The inventionfurther relates to fuel and lubricant compositions which comprise atleast one such Mannich adduct, and also a bisaminoalkylated Mannichadduct.

Direct-injection gasoline engines are becoming increasingly important,since, especially in the lean range, i.e. at a lambda value of about 1or greater, they enable better fuel utilization and a simultaneousincrease in the engine output. This is accompanied by reduced carbondioxide emission in comparison to conventional gasoline engines.

The injection nozzles in direct-injection gasoline engines are disposedin the combustion chamber and are therefore exposed to extremeconditions. Under these conditions, intense decomposition and oxidationof the fuel takes place and an increased amount of deposits forms.Deposition problems affect mainly the injection nozzles, but also theinlet valves and the entire combustion chamber. Deposits on theinjection nozzles restrict the fuel feed and change the injectionbehavior. A slightly reduced fuel feed can be compensated by appropriateelectronic control; stronger feed restriction and change in theinjection behavior can no longer be counteracted. However, for optimumfuel utilization and performance increase, impeccable injection behavioris essential. Therefore, the formation of deposits is to be avoided to avery substantial extent. In contrast to conventional engines in whichrelatively rich mixtures cause deposits, it is especially lean mixturesin direct-injection gasoline engines that lead to deposits.

WO 01/42399 describes the use of Mannich bases as fuel additives forpreventing deposits in direct-injection gasoline engines. Theinvestigations were carried out using Mannich bases which were based ona phenol substituted by a radical derived from a polyisobutene having alow reactivity, in a fuel-rich mixture (lambda value 0.8). However,commercially obtainable direct-injection gasoline engines work withrelatively fuel-lean mixtures, in order to achieve the requiredpetroleum savings. Also, a fuel-rich mixture, for example having alambda value of 0.8, would impair the function of a customary exhaustgas catalytic converter, and the maximum exhaust gas values laid down inlaw could be exceeded. The results achieved in WO 01/42399 are not yetsatisfactory; in particular, the Mannich bases described there fail onoperation of the engine within the lambda range of from 0.9 to 9. Also,the engine used there is not a modern direct injector, which can be seenfrom the use of an engine having flat top pistons. However, theconstruction of the cylinder does not correspond to the special cylindergeometry in modern direct injectors which is decisive for uniform fueldistribution.

It is an object of the present invention to provide suitable fueladditives which effectively prevent deposits in direct-injectiongasoline engines, even when operating the engine within the lambda rangeof from 0.9 to 9.

We have found that this object is achieved by the use of

-   -   a component A comprising at least one amine of the formula        NR¹R²R³ where    -   each R¹, R² and R³ is independently H, C₁-C₂₀-alkyl or        C₃-C₂₀-cycloalkyl, and two alkyl radicals together with the        nitrogen atom to which they are bonded may form a ring and the        alkyl and the cycloalkyl radicals may be interrupted by one or        more groups selected from O and NR⁴ and/or may be substituted by        one or more OR⁵ or NR⁶R⁷ groups where R⁴, R⁵, R⁶ and R⁷ are each        independently as defined for R¹, R² and R³, and/or    -   a component B comprising at least one Mannich adduct of the        formula I

-   -   where    -   R¹ and R² are each independently as defined for R¹, R² and R³ of        component A,    -   R⁸ is a polyisobutene radical which is preferably derived from        reactive polyisobutenes,    -   R⁹ is a C₁-C₆-alkyl group,    -   R¹⁰ is H or C₁-C₆-alkyl,    -   m is a number from 0 to (4-n) and    -   n is a number from 1 to 3,        as detergents and/or dispersants in fuel and lubricant        compositions for direct-injection gasoline engines which are        operated within a lambda range of from 0.9 to 9.

This use according to the invention is referred to hereinbelow as usevariant 1.

The operation of commercial direct-injection gasoline engines runsthrough cycles of different lambda values. In use variant 1, thecomponents A and/or B are used in fuel and lubricant compositions fordirect-injection gasoline engines in which the engine, in accordancewith the invention, is operated for more than 80% of the operating timeat a lambda value of at least 0.9 up to and including 9, preferably from0.95 to 8 and in particular from 0.97 to 6. The lambda value is theratio of the amount of air introduced into a combustion chamber to theamount of air theoretically required for complete combustion. A mixturehaving a lambda value of less than 1 is referred to as rich and onehaving a lambda value of greater than 1 is referred to as lean.

In use variant 1, the molecular weight of the amines NR¹R²R³ ofcomponent A or the sum of the molecular weights of the radicals NR¹R² inthe Mannich adduct I of component B is preferably from 120 to 1000 g/moland in particular from 180 to 600 g/mol. The molecular weight of theamines of component A is most preferably from 180 to 300 g/mol.

R⁸ is a polyisobutene radical which is preferably derived from“reactive” polyisobutenes. With regard to the definition of reactivepolyisobutenes and the preferred embodiments thereof, reference is madeto the remarks on R⁸ which follow.

The present invention further provides the use of

-   -   a component A comprising at least one amine of the formula        NR¹R²R³ where    -   each R¹, R² and R³ is independently H, C₁-C₂₀-alkyl or        C₃-C₂₀-cycloalkyl, and two alkyl radicals together with the        nitrogen atom to which they are bonded may form a ring and the        alkyl and the cycloalkyl radicals may be interrupted by one or        more groups selected from O and NR⁴ and/or may be substituted by        one or more OR⁵ or NR⁶R⁷ groups where R⁴, R⁵, R⁶ and R⁷ are each        independently as defined for R¹, R² and R³, with the proviso        that the molecular weight of the amine NR¹R²R³ is from 120 to        1000 g/mol and/or    -   a component B comprising at least one Mannich adduct of the        formula I

-   -   where    -   R¹ and R² are each independently as defined for R¹, R² and R³ of        component A, with the proviso that the sum of the molecular        weights of the radicals NR¹R² is from 120 to 1000 g/mol,    -   R⁸ is a poly(iso)butene radical,    -   R⁹ is a C₁-C₆-alkyl group,    -   R¹⁰ is H or C₁-C₆-alkyl,    -   m is a number from 0 to (4-n) and    -   n is a number from 1 to 3,        as detergents and/or dispersants in fuel and lubricant        compositions for direct-injection gasoline engines.

The use variant described here is referred to hereinbelow as use variant2.

Preferably in both variants component B is used alone or as a mixturewith component A.

In use variant 2, the molecular weight of the amines NR¹R²R³ ofcomponent A or the sum of the molecular weights of the radicals NR¹R² inthe Mannich adduct I of component B is preferably from 180 to 600 g/mol.The molecular weight of the amines of component A is more preferablyfrom 180 to 300 g/mol.

In use variant 2, the components A and/or B are used in fuel andlubricant compositions for direct-injection gasoline engines in whichthe engine is preferably operated for more than 80% of the operatingtime at a lambda value of preferably from 0.9 to 9, more preferably from0.95 to 8 and in particular from 0.97 to 6.

In both use variants 1 and 2, C₁-C₂₀-alkyl in the above definitions ofthe groups R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ is straight-chain or branchedalkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, 1-, 2- or 3-pentyl, 1-, 2-, 3- or4-methylbutyl, 1,1-, 1,2-, 1,3- or 2,2-dimethylpropyl, 1-, 2- or3-hexyl, 2-, 3- or 4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or3,3-dimethylbutyl, 2-ethylbutyl, 1-, 2-, 3- or 4-heptyl, 2-, 3-, 4- or5-methylhexyl, 1,1-, 1,2-, 1,3-, 1,4-, 2,2-, 2,3-, 2,4-, 3,3-, 3,4- or4,4-dimethylpentyl, 2- or 3-ethylpentyl, 1-, 2-, 3- or 4-octyl, 2-, 3-,4-, 5- or 6-methylhexyl, 1,1-, 1,2-, 1,3-, 1,4-, 1,5-, 2,2-, 2,3-, 2,4-,2,5-, 3,3-, 3,4-, 3,5-, 4,4-, 4,5- or 5,5-dimethylhexyl, 2-, 3- or4-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl. Thealkyl group may also be substituted by one or more C₃-C₂₀-cycloalkylradicals.

When 2 alkyl groups together with the nitrogen atom of the NR¹R² groupof the Mannich adduct I or of the amine NR¹R²R³ form a ring, in whichcase the alkyl group may be interrupted by an O or NR⁴ moiety, the ringis, for example, piperidine, piperazine or morpholine.

In the above definitions of the groups R¹, R², R³, R⁴, R⁵, R⁶ and R⁷,the C₃-C₂₀-cycloalkyl group is, for example, cyclopropyl, cyclopentyl,cyclohexyl, cyclooctyl or cyclodecyl. The cycloalkyl group may besubstituted by one or more C₁-C₂₀-alkyl groups. Examples thereof are3-methylcyclopentyl and 4-methylcyclohexyl.

In the above definition of the groups R⁹ and R¹⁰, C₁-C₆-alkyl is inparticular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 1-, 2- or 3-pentyl, 1-, 2-, 3- or 4-methylbutyl,1,1-, 1,2-, 1,3- or 2,2-dimethylpropyl, 1-, 2- or 3-hexyl, 2-, 3- or4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl or2-ethylbutyl.

The radicals R¹, R² and R³ are preferably each independently branched orunbranched C₆-C₂₀-alkyl, such as 1-, 2- or 3-hexyl, 2-, 3- or4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl,2-ethylbutyl, 1-, 2-, 3- or 4-heptyl, 2-, 3-, 4- or 5-methylhexyl, 1,1-,1,2-, 1,3-, 1,4-, 2,2-, 2,3-, 2,4-, 3,3-, 3,4- or 4,4-dimethylpentyl, 2-or 3-ethylpentyl, 1-, 2-, 3- or 4-octyl, 2-, 3-, 4-, 5- or6-methylhexyl, 1,1-, 1,2-, 1,3-, 1,4-, 1,5-, 2,2-, 2,3-, 2,4-, 2,5-,3,3-, 3,4-, 3,5-, 4,4-, 4,5- or 5,5-dimethylhexyl, 2-, 3- or4-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl,C₆-C₂₀-cycloalkyl, such as cyclohexyl, cyclooctyl or cyclodecyl, or

CR¹¹R¹²)_(x)—NR⁴

_(Y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),

CR¹¹R¹²)_(x)—O

_(Y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (III) or

CR¹¹R¹²)_(x)—NR⁴

_(Y)(CR¹³R¹⁴)_(z)—OR⁵  (IV)where R⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are each independently H orC₁-C₆-alkyl,R⁶ and R⁷ are each independently H, C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl,x and z are each independently a number from 1 to 20 andy is a number from 0 to 10.

In the above definition of the groups R⁴, R⁵, R⁶, R⁷, R¹¹, R¹², R¹³ andR¹⁴, C₁-C₆-alkyl is in particular methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, 1-, 2- or 3-pentyl, 1-, 2-, 3-or 4-methylbutyl, 1,1-, 1,2-, 1,3- or 2,2-dimethylpropyl, 1-, 2- or3-hexyl, 2-, 3- or 4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or3,3-dimethylbutyl or 2-ethylbutyl.

R¹¹, R¹², R¹³ and R¹⁴ are preferably each H.

In both use variants 1 and 2, suitable amines of component A are bothmonoamines, i.e. amines having only one amine function in the molecule,and polyamines, i.e. amines having at least two amine functions in themolecule. If component A is an alkylamine, especially a monoalkylamine,it is preferably not used alone in both variants. Especially linearmonoalkylamines are not used alone.

Suitable monoamines are both primary and secondary or tertiary amines.Primary amines are those in which two of the R¹, R² and R³ radicals areeach H. For both use variants 1 and 2, examples of suitable primarymonoamines are octylamine, 2-ethylhexylamine, nonylamine, decylamine,undecylamine, dodecylamine, tridecylamine, tetradecylamine,pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine,nonadecylamine, eicosylamine, and also cyclooctylamine andcyclodecylamine. In use variant 1, further suitable primary amines aremethylamine, ethylamine, propylamine, butylamine, pentylamine,hexylamine and heptylamine. Secondary amines are those in which one ofthe R¹, R² and R³ radicals is H. For both use variants 1 and 2, examplesof suitable secondary monoamines are dibutylamine, diisobutylamine,di-tert-butylamine, dipentylamine, dihexylamine, diheptylamine,dioctylamine, di(2-ethylhexylamine), dinonylamine and didecylamine, andalso N-methylcyclohexylamine, N-ethylcyclohexylamine anddicyclohexylamine. In use variant 1, further suitable secondary aminesare dimethylamine, diethylamine, dipropylamine and diisopropylamine.Tertiary amines are those in which none of the three R¹, R² and R³radicals is H. For both use variants 1 and 2, examples of suitabletertiary amines are tripropylamine, triisopropylamine, tributylamine,tripentylamine, trihexylamine, triheptylamine, trioctylamine,trinonylamine and tridecylamine, and also N-methyldicyclohexylamine andN-ethyldicyclohexylamine. In use variant 1, further suitable tertiaryamines are trimethylamine and triethylamine. Also suitable are allisomers of the abovementioned amines. Preferred monoamines are secondaryamines, in particular those in which the two radicals which are not Hare the same. Preference is given to using mixtures of monoamines, inparticular amine mixtures which are accessible on the industrial scale,such as fatty amines, as described, for example, in Ullmann'sEncyclopedia of Industrial Chemistry, 6th edition, 2000, electronicrelease, “Amines, aliphatic”, which is fully incorporated herein by wayof reference.

Examples of suitable cyclic monoamines for use variant 1 arepyrrolidine, piperidine and morpholine.

Suitable polyamines for both use variants 1 and 2 are amines of theformula NR¹R²R³ where at least one of the R¹, R² or R³ radicals is aradical of the formula II, III or IV

CR¹¹R¹²)_(x)—NR⁴

_(y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),

CR¹¹R¹²)_(x)—O

_(Y)(CR¹³R¹³)_(z)—NR⁶R⁷  (III)

CR¹¹R¹²)_(x)—NR⁴

_(Y)(CR¹³R¹⁴)_(z)—OR⁵  (IV)whereR⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are each independently H or C₁-C₆-alkyl;R⁶, R⁷, R¹⁵ and R¹⁶ are each independently H, C₁-C₆-alkyl orC₁-C₆-hydroxyalkyl,x and z are each independently a number from 1 to 20 andy is a number from 0 to 10, although y may not be 0 in formula IV.

The polyamine used is preferably an amine in which at least one R¹, R²or R³ radical is a radical of the formula II. Preference is given toradicals II in which R⁴, R¹¹, R¹², R¹³ and R¹⁴ are each H, x and z are anumber from 1 to 8 and y is a number from 0 to 10. Examples of suchpolyamines are triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine,tetrapropylenepentamine, dibutylenetriamine, tributylenetetramine,tetrabutylenepentamine, N,N-dipropylmethylenediamine,N,N-dipropylethylene-1,2-diamine, N,N-diethylpropylene-1,3-diamine,N,N-dipropylpropylene-1,3-diamine, N,N-diethylbutylene-1,4-diamine,N,N-dipropylbutylene-1,4-diamine, N,N-dimethylpentylene-1,3-diamine,N,N-diethylpentylene-1,5-diamine, N,N-dipropylpentylene-1,5-diamine,N,N-dimethylhexylene-1,6-diamine, N,N-diethylhexylene-1,6-diamine,N,N-dipropylhexylene-1,6-diamine, bis[2-(N,N-dimethyl-amino)ethyl]amine,bis[2-(N,N-dipropylamino)ethyl]amine,bis[3-(N,N-dimethylamino)propyl]amine,bis[3-(N,N-diethylamino)-propyl]amine,bis[3-(N,N-dipropylamino)propyl]amine,bis[4-(N,N-dimethylamino)butyl]amine,bis[4-(N,N-diethylamino)butyl]amine,bis[4-(N,N-dipropylamino)butyl]amine,bis[5-(N,N-dimethylamino)-pentyl]amine,bis[5-(N,N-diethylamino)pentyl]amine,bis[5-(N,N-dipropylamino)pentyl]amine,bis[6-(N,N-dimethylamino)-hexyl]amine,bis[6-(N,N-diethylamino)hexyl]amine,bis[6-(N,N-dipropylamino)hexyl]amine,tris[2-(N,N-dimethyl-amino)ethyl]amine,tris[2-(N,N-dipropylamino)ethyl]amine,tris[3-(N,N-dimethylamino)propyl]amine,tris[3-(N,N-diethyl-amino)propyl]amine,tris[3-(N,N-dipropylamino)propyl]amine,tris[4-(N,N-dimethylamino)butyl]amine,tris[4-(N,N-diethylamino)-butyl]amine,tris[4-(N,N-dipropylamino)butyl]amine,tris[5-(N,N-dimethylamino)pentyl]amine,tris[5-(N,N-diethyl-amino)pentyl]amine,tris[5-(N,N-dipropylamino)pentyl]amine,tris[6-(N,N-dimethylamino)hexyl]amine,tris[6-(N,N-diethylamino)-hexyl]amine,tris[6-(N,N-dipropylamino)hexyl]amine and the like. In use variant 1,also suitable are ethylenediamine, diethylenetriamine andN,N-dimethylpropylene-1,3-diamine. Among these, preference is given inboth use variants 1 and 2 to triethylenetetramine,tetraethylenepentamine and bis[3-N,N-dimethylamino)propyl]amine. In usevariant 1, preference is further given to diethylenetriamine andN,N-dimethylpropylene-1,3-diamine.

Examples of suitable cyclic polyamines for both use variants arediethylpiperazine andN,N′,N″-tris(N,N-dimethylamino)propyl-hexahydrosymtriazine.

In both use variants 1 and 2, R⁹ in the Mannich adduct I of component Bis preferably a C₁-C₄-alkyl group, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Particularpreference is given to R⁹ being methyl or ethyl, in particular methyl.

Depending on the number of (CHR¹⁰—NR¹R²) radicals (i.e. on n), thevariable m is a number from 0 to (4-n). Preferably, m is a number from 0to 2, more preferably 0 or 1 and especially 0.

R¹⁰ is H or C₁-C₆-alkyl, preferably H.

R¹ and R² are each independently H, C₁-C₂₀-alkyl or C₃-C₂₀-cycloalkyl,and two alkyl radicals may also together form a ring with the nitrogenatom to which they are bonded and the alkyl and cycloalkyl radicals asdescribed above may be interrupted by one or more O or NR⁴ groups and/ormay be substituted by one or more OR⁵ or NR⁶R⁷ groups where R⁴, R⁵, R⁶and R⁷ are each independently as defined for R¹ and R². It is essentialto the invention in use variant 2 that the sum of the molecular weightof n NR¹R² radicals is from 120 to 1000 g/mol, preferably from 180 to600 g/mol and more preferably from 230 to 600 g/mol. In order to fulfilthis proviso, R¹ and R² in use variant 2 must not at the same time be H.In use variant 1, the sum of the molecular weight of n NR¹R² radicals ispreferably from 120 to 1000 g/mol, particularly preferably from 120 to800 g/mol, more preferably from 180 to 600 g/mol and in particular from230 to 600 g/mol. R¹ and R² are preferably not both H at the same time.

In both use variants 1 and 2, R¹ and R² are preferably eachindependently H, C₆-C₂₀-alkyl, C₆-C₂₀-cycloalkyl or a radical of thefollowing formulae II to IV

CR¹¹R¹²)_(x)—NR⁴

_(y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),

CR¹¹R¹²)_(x)—O

_(Y)(CR¹³R¹³)_(z)—NR⁶R⁷  (III) and

CR¹¹R¹²)_(x)—NR⁴

_(Y)(CR¹³R¹⁴)_(z)—OR⁵  (IV)whereR⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are each independently H or C₁-C₆-alkyl;R⁶ and R⁷ are each independently H, C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl,x and z are each independently a number from 1 to 20, preferably from 1to 6, andy is a number from 0 to 10.

R¹¹, R¹², R¹³ and R¹⁴ are preferably each H.

R⁴ and R⁵ are preferably each H or C₁-C₆-alkyl, more preferably H ormethyl.

R⁶ and R⁷ are preferably each H, methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, hydroxymethyl,2-hydroxyethyl or 3-hydroxypropyl and more preferably methyl.

R¹ and R² are preferably each the same radical. In a particularlypreferred embodiment, both R¹ and R² are a radical of the formula IIwhere y is 0, z is a number from 3 to 6, R¹³ and R¹⁴ are each H and bothR⁶ and R⁷ are each methyl, ethyl, propyl, hydroxymethyl or hydroxyethyl.z is especially 3 and R⁶ and R⁷ are methyl, i.e. NR¹R² is especiallyN[(CH₂)₃N(CH₃)₂]₂.

In a further preferred embodiment, R¹ and R² are each a C₆-C₁₀-alkylradical, such as 1-, 2- or 3-hexyl, 2-, 3- or 4-methylpentyl, 1,1-,1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl, 2-ethylbutyl, 1-, 2-, 3- or4-heptyl, 2-, 3-, 4- or 5-methylhexyl, 1,1-, 1,2-, 1,3-, 1,4-, 2,2-,2,3-, 2,4-, 3,3-, 3,4- or 4,4-dimethylpentyl, 2- or 3-ethylpentyl, 1-,2-, 3- or 4-octyl, 2-, 3-, 4-, 5- or 6-methylhexyl, 1,1-, 1,2-, 1,3-,1,4-, 1,5-, 2,2-, 2,3-, 2,4-, 2,5-, 3,3-, 3,4-, 3,5-, 4,4-, 4,5- or5,5-dimethylhexyl, 2-, 3- or 4-ethylhexyl, nonyl or decyl, morepreferably a C₈-alkyl radical and especially 2-ethylhexyl. R¹ and R² arepreferably each the same radical.

n is a number from 1 to 3, preferably a number from 1 to 2 and inparticular 2.

The proviso essential to the invention in use variant 2 that the sum ofthe molecular weights of the NR¹R² radicals should be from 120 to 1000should be interpreted in such a way that the molecular weight of oneNR¹R² radical in n identical (CHR¹⁰—NR¹R²) radicals is from 120/n to1000/n. Correspondingly, suitable NR¹R² radicals are dependent upon thetotal number n of (CHR¹⁰—NR¹R²) radicals with regard to the molecularweight. In the case of different (CHR¹⁰—NR¹R²) radicals in the Mannichadduct I, the weight-averaged value of the molecular weight of nradicals is from 120 to 1000 g/mol. The same applies correspondingly inthe preferred embodiment of use variant 1, in which the sum of themolecular weights of the NR¹R² radicals is from 120 to 1000.

In both use variants 1 and 2, Mannich adducts of the formula I areobtainable, for example, by the reaction of a phenol, substituted by apolyolefin radical R⁸, of the formula V

where R⁸, R⁹ and m are each as defined in the particular use variants 1and 2,in a Mannich(-like) reaction with an aldehyde CHR¹⁰O and an amine NHR¹R²where R¹⁰, R¹ and R² are each as defined above. With regard to thepreferred reactants V, aldehyde and amine, the remarks made in theparticular use variants on R⁸, R⁹, R¹⁰, R¹, R² and n and also theremarks below on R⁸ apply.

Suitable aldehydes CHR¹⁰O are formaldehyde, acetaldehyde,propionaldehyde and butyraldehyde or compounds from which thesealdehydes are accessible. These are referred to generally hereinbelow asaldehyde sources. Preference is given to using formaldehyde. Suitableformaldehyde sources are formaldehyde gas, formalin solutions,formaldehyde oligomers such as trioxane or tetraoxane and polymers offormaldehyde such as paraformaldehyde. Preference is given to usingparaformaldehyde or formalin solution.

The phenol V can be converted to the Mannich adducts I in two differentways. In the first, it can be reacted at the same time with the aldehydeand the amine NHR¹R². Preferably, the amine in this reaction variant(variant A) has no primary amino function, since relatively largeamounts of undesired oligomerization products would otherwise occur. Forthe purposes of this invention, primary amino functions are those of theformula NH₂R, where R is a substituent other than hydrogen. In thesecond, the phenol V can be reacted with an adduct of an aldehyde and anamine of the formula NHR¹R² prepared beforehand (variant B). In thiscase, the amine can also have a primary amino function, i.e. one of theR¹ or R² radicals can be H.

The remarks made above on R¹ and R² apply for suitable amines NHR¹R².Examples of amines in which R¹ and/or R² is C₁-C₂₀-alkyl includepropylamine, isopropylamine, butylamine, pentylamine, hexylamine,heptylamine, octylamine, diethylamine, dipropylamine, diisopropylamine,dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine,di(2-ethylhexyl)amine, dinonylamine and didecylamine. Examples ofsuitable amines in which R¹ and/or R² is/are each a radical of theformula II are diethylenetriamine, triethylenetetramine,tetraethylenepentamine, pentaethylenehexamine, propylenediamine,dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine,butylenediamine, dibutylenetriamine, tributylenetetramine,tetrabutylenepentamine, N,N-dimethylmethylenediamine,N,N-diethylmethylenediamine, N,N-dipropylmethylenediamine,N,N-dimethylethylene-1,2-diamine, N,N-diethylethylene-1,2-diamine,N,N-dipropylethylene-1,2-diamine, N,N-dimethylpropylene-1,3-diamine,N,N-diethylpropylene-1,3-diamine, N,N-dipropylpropylene-1,3-diamine,N,N-dimethylbutylene-1,4-diamine, N,N-diethylbutylene-1,4-diamine,N,N-dipropylbutylene-1,4-diamine, N,N-dimethylpentylene-1,3-diamine,N,N-diethylpentylene-1,5-diamine, N,N-dipropylpentylene-1,5-diamine,N,N-dimethylhexylene-1,6-diamine, N,N-diethylhexylene-1,6-diamine,N,N-dipropylhexylene-1,6-diamine, bis[(N,N-dimethylamino)methyl]amine,bis[(N,N-diethylamino)methyl]amine,bis[(N,N-dipropylamino)-methyl]amine,bis[2-(N,N-dimethylamino)ethyl]amine,bis[2-(N,N-dipropylamino)ethyl]amine,bis[3-(N,N-dimethylamino)-propyl]amine,bis[3-(N,N-diethylamino)propyl]amine,bis[3-(N,N-dipropylamino)propyl]amine,bis[4-(N,N-dimethylamino)-butyl]amine,bis[4-(N,N-diethylamino)butyl]amine,bis[4-(N,N-dipropylamino)butyl]amine,bis[5-(N,N-dimethylamino)-pentyl]amine,bis[5-(N,N-diethylamino)pentyl]amine,bis[5-(N,N-dipropylamino)pentyl]amine,bis[6-(N,N-dimethyl-amino)hexyl]amine,bis[6-(N,N-diethylamino)hexyl]amine,bis[6-(N,N-dipropylamino)hexyl]amine and the like. Also suitable forpreparing the Mannich adducts I used in use variant 1 are methylamine,ethylamine, dimethylamine and ethylenediamine.

Particularly preferred amines are bis[3-(N,N-dimethylamino)-propyl]amineand di(2-ethylhexyl)amine.

The reaction temperatures suitable for the reaction of variant A dependon a series of factors. Water of reaction is formed in the Mannichreaction in variant A. In general, this is removed from the reactionmixture. The water of reaction can be removed during the reaction, atthe end of the reaction time or on completion of reaction, for exampledistillatively. Advantageously, the water of reaction can be removed byheating the reaction mixture in the presence of azeotroping agents.Examples of suitable azeotroping agents are organic solvents which forman azeotrope with water and/or have a boiling point above the boilingpoint of water.

Particularly suitable azeotroping agents are benzene and alkylaromatics, in particular toluene, xylenes and mixtures of alkylaromatics with other (high-boiling) hydrocarbons. It is particularlysimple to use certain distillation fractions of crude oil which aregenerally sold according to flash point or boiling range or elsearomatics content. Examples thereof are the Solvesso and the Risellabrands. In general, the removal of the water of reaction is carried outat a temperature which corresponds approximately to the boiling point ofthe azeotroping agent or of the azeotrope composed of water andazeotroping agent.

Suitable temperatures for the removal of the water of reaction atatmospheric pressure are therefore in the range from 75 to 200° C.,preferably from 80 to 180° C., and more preferably in the range from 80to 150° C. When the water of reaction is removed under reduced pressure,the temperatures should be reduced in accordance with the reducedboiling temperatures.

The reaction temperatures for the Mannich reaction in variant A arepreferably in the range from 10 to 200° C., in particular in the rangefrom 20 to 180° C., for example about 35° C., about 90° C., about 120°C., 140° C. or about 160° C.

The reaction in variant A can, for example, be carried out in such a waythat phenol, amine and aldehyde source are combined and the reactionmixture is brought to the desired reaction temperature, preferablywithin the abovementioned temperature ranges. The reaction can also becarried out in such a way that the phenol and optionally a solvent arefirst admixed with the aldehyde source and optionally heated to thereaction temperature and at least one secondary amine is subsequentlyadded. The amine can be added in one portion or over a period of, forexample, from 5 to 300 minutes by repeated addition in portions orcontinuous addition. The reaction can also be carried out in such a waythat first phenol V and any solvent and amine are added, optionallyheated to reaction temperature and subsequently admixed with thealdehyde source, and the aldehyde source can be added as described abovefor the amine.

In a preferred embodiment, variant A, i.e. the Mannich reaction and theremoval of the water of reaction, is carried out, for instance, atatmospheric pressure and a temperature of about 80° C., about 110° C. orabout 130° C. using aromatic solvents, preferably toluene, xylenes ormixtures thereof, as azeotroping agents. Variant A is preferably carriedout in such a way that the reactants are combined within a temperaturerange between 10 and 50° C., optionally mixed within this temperaturerange and subsequently brought to the temperature required todistillatively remove the water of reaction.

The total reaction time for the conversion of the phenols V to theMannich adducts I can be selected by those skilled in the art dependingon the reaction parameters such as temperature and amounts of reactants,and is generally between 10 minutes and 24 hours.

To prepare the Mannich adducts I used in use variant 2, the reactants invariants A or B of the Mannich reaction are used in ratios which dependin use variant 2 on the molecular weight of the amine used.

If the molecular weight of the amine is 120 g/mol or less, the reactantratio has to be selected in such a way that a bisaminoalkylated phenol Ican be formed, in order to fulfill the proviso essential to theinvention in use variant 2 with regard to the molecular weight of nNHR¹R² radicals. Accordingly, the molar ratio of phenol V to amine toaldehyde is generally 1:2-3:2-3, preferably 1:2.0-2.5:2.0-2.5, morepreferably about 1:2:2.

If the molecular weight of the amine used is at least 121 g/mol, thereactant ratio can be selected in such a way that, depending on thedesired degree of aminomethylation, mono- or bisaminoalkylated phenols Ican be formed, because the abovementioned proviso regarding themolecular weight in use variant 2 is in this case fulfilled even in thecase of a single aminoalkylated phenol. Accordingly, the ratio of phenolV to amine to aldehyde is suitably 1:0.8-3.0:0.8-3.0, preferably1:1.0-2.5:1.0-2.5 and more preferably about 1:1.0-2.0:1.0-2.0.

In a particularly preferred embodiment, the ratio of phenol v to amineto aldehyde is about 1:2:2, irrespective of the type of amine selected.

To prepare the Mannich adducts used in use variant 1, these reactantratios are not obligatory, but preferred.

In variant B, an adduct is initially prepared from aldehyde or analdehyde equivalent, such as dichloromethane or dibromomethane ordimethoxymethane, amine, and optionally solvent by combining thecomponents, optionally with heating to temperature ranges describedabove for variant A and within the reaction times described above forvariant A. During or after the reaction of amine and aldehyde source,water of reaction formed may, if desired, be removed, for example asdescribed above. The reaction product obtained in this way from amineand aldehyde may, if desired, be purified and/or isolated. The adductsin particular which are obtainable by reacting one equivalent ofaldehyde or one equivalent of an aldehyde equivalent with one or twoequivalents of a secondary amine or one equivalent of a primary amineafter removing the water of reaction, alcohol or halide formed(secondary amine: alkyleneiminium ion or aminal; primary amine: imine orhexahydrotriazine) can, if desired, be isolated, purified and/or storedfor a later reaction with the phenol V. Subsequently, the reactionproduct of amine and aldehyde or aldehyde equivalent and the phenol Vare admixed together, and they may be combined in one portion, in aplurality of portions or continuously, within the abovementionedperiods. Reaction temperatures and reaction times are typically withinthe ranges as described above for the reactions of variant A. When thereaction product of aldehyde or aldehyde equivalent and amine isisolated, the reaction with the phenol V is preferably carried out insuch a way that the phenol and any solvents are initially charged, theinitial charge is optionally heated to a temperature within the rangefrom 50 to 180° C. and the adduct of amine and aldehyde or aldehydeequivalent is subsequently added. The reaction mixture is then heated toa suitable reaction temperature. If desired, the amine formed in thereaction of aminals with the phenol may, depending on the volatility ofthe amine, be distilled off and/or removed under reduced pressure.

When the reaction described under variant B without isolation of theadduct of aldehyde or aldehyde equivalent and amine(s) is carried out,preference is given to first combining the aldehyde source or thealdehyde equivalent and amine, optionally heating and mixing andadmixing the adduct with the phenol V. To this end, preference is givento adding the phenol V to the adduct in the initial charge and heatingthe mixture to a suitable reaction temperature. Suitable reactiontemperatures therefor are, for example, in the range from 25 to 120° C.and in particular in the range from 50 to 100° C.

According to variant B, when using primary amines, the adduct used ispreferably an imine or N-substituted hexahydrotriazine which hasoptionally been isolated beforehand and whose substituents are derivedfrom the abovementioned R¹ or R² radicals.

According to variant B, when using secondary amines, the adduct used ispreferably a hemiaminal, alkyleneiminium ion or aminal, each of whichhas optionally been isolated beforehand, and the amino functions of thehemiaminal, alkyleneiminium ion or aminal are preferably derived fromthe abovementioned secondary amines HNR¹R².

In variant B, the adduct used is preferably an adduct of at least oneamine and an aldehyde source, said adduct being obtainable by processesknown per se. To this end, the reactants are advantageously reactedtogether at a temperature above 0° C., preferably above +20° C., forexample within a temperature range of from 20 to 30° C. or from about 20to 50° C. Optionally, water of reaction formed can subsequently beremoved under the conditions described above for variant A, for exampledistillatively.

Suitable solvents for the reaction of variant B are the solvents andazeotroping agents described for the reaction of variant A and alsohydrocarbons and hydrocarbon mixtures having boiling points or rangesbetween +35 and +110° C., alcohols, C₂-C₆-dialkyl ethers, cyclic mono-and diethers having from 3 to 6 carbon atoms, in particular ethanol,isopropanol, butanols, tetrahydrofuran, tetrahydropyran and dioxane.

In variant B, the adduct used is preferably an aminal of the aldehydewith a secondary amine as defined above.

Suitable aminals for the above-described reaction are, for example,N,N,N′,N′-tetramethylmethylenediamine andN,N,N′,N′-tetraethylmethylenediamine.

In a further embodiment of variant B, the phenols V can be reacted in ananalogous reaction with hemiaminals to give Mannich adducts. Suchhemiaminals are obtainable from aldehyde sources or aldehyde equivalentsand secondary amines which have no primary amino function and can beobtained in a one-pot reaction in the presence of the phenols V (variantA) or separately (variant B).

By means of the procedures described above under variant A and variantB, the phenol V can be converted to mono- and bisaminoalkylated Mannichadducts by choosing the stoichiometry.

In a preferred embodiment, the aldehyde source or the aldehydeequivalent, preferably formalin solution or paraformaldehyde, optionallyin solvent, is first initially charged, and an approximately equimolaramount of a secondary amine, preferably of an amine having only onesecondary and no primary amino group, is added at a temperature withinthe range from +15 to +50° C., preferably from +20 to +35° C.Subsequently, the mixture is mixed at a temperature within theabove-specified range and then combined with the phenol V and optionallyfurther solvent. Subsequently, the mixture obtained in this way isheated to a temperature within the range from 40 to 100° C., preferablyfrom 50 to 90° C., for example under reflux. Subsequently, the reactionmixture may, if desired, be purified, for example by filtering and/orremoving the volatile constituents, for example under reduced pressureor by distillation.

In a further preferred embodiment, the phenol V is optionally initiallycharged in a solvent and the mixture is heated to a temperature in therange from 40 to 100° C., preferably from 50 to 90° C., for exampleunder reflux of the solvent. Subsequently, either an approximatelyequimolar amount or from 1.7 to 2.5 equivalents, for example about 2equivalents, of an aminal, optionally in a solvent, are added slowly atthis temperature and the reaction mixture is allowed to react for afurther 30 minutes to 4 hours, in particular from 1 to 3 hours, at atemperature in the abovementioned ranges. The reaction mixture canoptionally be subsequently purified, for example by filtering and/orremoving the volatile constituents under reduced pressure or bydistillation.

Suitable solvents for the two above-described embodiments of variant Bare hydrocarbons, hydrocarbon mixtures, ethers or alcohols, each havinga boiling point or boiling range in the range from 40 to 100° C., inparticular from 50 to 90° C. Especially suitable are tetrahydrofuran anddioxane.

In a further preferred embodiment, first the phenol V and optionallysolvent are initially charged. Subsequently, an approximately equimolaramount or preferably from 1.7 to 2.5 equivalents, for example about 2equivalents, of an aldehyde source and of a preferably secondary amine,more preferably an amine without primary and without further secondaryamino functions, and optionally solvent, is added slowly, for example bydropwise addition. Subsequently, the components are mixed and themixture is then heated to a temperature in the range from 40 to 100° C.,preferably from 50 to 90° C. The reaction mixture may subsequently bepurified, for example by filtering and/or removing the volatileconstituents under reduced pressure or by distillation. Suitable assolvents are in particular the solvents specified in the above-describedpreferred embodiments. Preference is given to isopropanol.

In a further preferred embodiment, phenol V and an approximatelyequimolar amount or preferably from 1.7 to 2.5 equivalents, for exampleabout 2 equivalents, of a preferably secondary amine, more preferably anamine without primary and without further secondary amino functions, areinitially charged in solvent. Subsequently, an approximately equimolaramount of an aldehyde source is added slowly. Preference is given toheating the reaction mixture during the addition of the aldehyde sourceto a temperature in the range from 30 to 70° C., preferably from 40 to60° C. Subsequently, the reaction mixture is heated to a temperature inthe range from 80 to 180° C., preferably from 90 to 140° C., and morepreferably to reflux of the solvent. This preferably distillativelyremoves the water of reaction formed. Suitable solvents for thisembodiment are in particular aromatic solvents or mixtures thereof withfurther high-boiling hydrocarbons. Particularly suitable are xylenes andtoluene and mixtures thereof.

In general, the above-described process provides a Mannich adductmixture which comprises at least 40 mol %, frequently at least 50 mol %and more preferably at least 60 mol %, of compounds of the formula I.The compounds I can be isolated from the reaction mixture and fed to theuse according to the invention. However, it is equally possible inaccordance with the invention to use the compounds I in the form of theentire reaction mixture which is obtained from the process describedabove.

In the definition of R⁸ in use variant 2, the poly(iso)butene radical ispreferably the homo- or copolymer radical which is obtainable by homo-or copolymerization of 1-butene, 2-butene and/or isobutene. R⁸ in usevariant 2 is more preferably a polyisobutene radical.

In both use variants 1 and 2, the radical R⁸ is in particular a radicalwhich is derived from “reactive” polyisobutenes which differ from the“low-reactivity” polyisobutenes by the content of terminal double bonds.Reactive polyisobutenes differ from low-reactivity polyisobutenes inthat they have at least 50 mol %, based on the total number ofpolyisobutene macromolecules, of terminal double bonds. In both usevariants 1 and 2, the reactive polyisobutenes preferably have at least60 mol % and more preferably at least 80 mol %, based on the totalnumber of polyisobutene macromolecules, of terminal double bonds. Theterminal double bonds may either be vinyl double bonds [—CH═C(CH₃)₂] orvinylidene double bonds [—CH₂—C(═CH₂)—CH₃]. Phenols substituted byreactive polyisobutenes and processes for preparing them are describedin DE-A-19948111, which is fully incorporated herein by way ofreference. In both use variants 1 and 2, preference is given inparticular to polyisobutenes which have uniform polymer frameworks.Uniform polymer frameworks are possessed in particular by thosepolyisobutenes which are composed of at least 85% by weight, preferablyof at least 90% by weight and more preferably of at least 95% by weight,of isobutene units. Furthermore, the reactive polyisobutenes preferablyhave a polydispersity of less than 3.0, in particular less than 1.9 andmore preferably less than 1.7 or less than 1.5. Polydispersity is thequotient of the weight-average molecular weight M_(W) divided by thenumber-average molecular weight M_(N).

R⁸ preferably has a number-average molecular weight in the range from300 to 3000, more preferably from 400 to 2500, for example anumber-average molecular weight of about 550, about 800, about 1000 orabout 2300, and most preferably from 500 to 1500, for example anumber-average molecular weight of about 550, about 800 or about 1000.

In both use variants 1 and 2, particularly suitable reactivepolyisobutenes are, for example, the Glissopal brands from BASF AG, inparticular Glissopal 1000 (M_(N)=1000), Glissopal 550 (M_(N)=550) andGlissopal 2300 (M_(N)=2 300) and mixtures thereof. Other number-averagemolecular weights can be attained by a manner known in principle bymixing polyisobutenes of different number-average molecular weights orby extractive enrichment of polyisobutenes of certain molecular weightranges.

R⁸ is preferably in the p-position to the OH group.

The polyisobutene-substituted phenol V is obtainable, for example, bythe reaction (alkylation) of a phenol substituted by m R⁹ radicals withsuch a polyisobutene. Suitable for the reaction with reactivepolyisobutenes are unsubstituted phenol and mono- or disubstitutedphenols. Suitable substituted phenols are in particularmono-ortho-substituted phenols. Suitable alkyl-substituted phenols are2-methylphenol and 2-ethylphenol. Particularly preferred for thealkylation with polyisobutenes are unsubstituted phenol and2-methylphenol.

In the alkylation, the phenol is customarily used in an equimolar amountor in excess. Suitable is from about a 1.1- to 10-fold excess, forexample an about 1.1-fold, an about 2-fold, an about 4-fold or an about6-fold, excess of the phenol. The crude product obtained is optionallyfurther reacted after purification, for example as described above in aMannich(-like) reaction.

After completed reaction, the reaction mixture can be freed of excessphenol and/or catalyst, for example, by extraction with solvents,preferably polar solvents, such as water or C₁-C₆-alkanols or mixturesthereof, for example by stripping, i.e. by passing through steam oroptionally heating of gases, for example nitrogen, distillatively or bybasic ion exchangers, as described in the German patent application P10060902.3.

The alkylation of the phenol is carried out below about 60° C.,preferably below 40° C. and in particular below 30° C., in the presenceof an alkylation catalyst. In general, the alkylation is carried out attemperatures above −40° C., preferably above −30° C. and in particularabove −20° C. Particularly suitable for the alkylation are temperaturesin the range from −10 to +45° C., in particular in the range from 0 to+40° C. and more preferably from 10 to +35° C.

Suitable alkylation catalysts are known to those skilled in the art.Suitable are, for example, protic acids such as sulfuric acid,phosphoric acid and organic sulfonic acids, e.g.trifluoromethanesulfonic acid, Lewis acids such as aluminum trihalides,e.g. aluminum trichloride or aluminum tribromide, boron trihalides, e.g.boron trifluoride and boron trichloride, tin halides, e.g. tintetrachloride, titanium halides, e.g. titanium tetrabromide and titaniumtetrachloride; and iron halides, e.g. iron trichloride and irontribromide. The Lewis acids are optionally used together with Lewisbases such as alcohols, in particular C₁-C₆-alkanols, phenols oraliphatic or aromatic ethers, for example diethyl ether, diisopropylether or anisol. Preference is given to adducts of boron trihalides, inparticular boron trifluoride, in combination with the abovementionedLewis bases. Particular preference is given to boron trifluorideetherate and boron trifluoride phenolate. For practical reasons, thelatter is particularly suitable, since it is formed in the phenolicreaction mixture when introducing boron trifluoride.

Preference is given to carrying out the alkylation in a liquid medium.To this end, the phenol is preferably dissolved in one of the reactantsand/or a solvent, optionally with heating. In a preferred embodiment,the alkylation is therefore carried out in such a way that the phenol orthe substituted phenol is first melted with the introduction of heat andsubsequently admixed with a suitable solvent and/or the alkylationcatalyst, in particular the boron trihalide adduct. Afterwards, theliquid mixture is brought to a suitable reaction temperature. In afurther preferred embodiment, the phenol is first melted and admixedwith the polyisobutene and optionally a suitable solvent. The liquidmixture obtained in this way can be brought to a suitable reactiontemperature and subsequently admixed with the alkylation catalyst.

Suitable solvents for the performance of this reaction are, for example,hydrocarbons, preferably pentane, hexane and heptane, in particularhexane, hydrocarbon mixtures, for example benzines having boiling rangesbetween 35 and 100° C., kerosene fractions having boiling ranges of from100 to 200° C., aromatic hydrocarbons such as toluene, ethylbenzene,propyl- and isopropylbenzene, n-butylbenzene, sec-butylbenzene,isobutylbenzene, tert-butylbenzene or the xylenes and also mixturesthereof, for example in the form of commercial alkyl aromaticsfractions, such as Solvesso 100, 150 or 200, and halogenatedhydrocarbons, such as dichloromethane or trichloromethane, and alsomixtures of the abovementioned solvents.

The reaction is preferably initiated by adding the catalyst or one ofthe two reactants, phenol or polyisobutene. The component initiating thereaction is preferably added over a period of from 2 to 300 minutes,preferably from 5 to 200 minutes and in particular from 10 to 180minutes, and the temperature of the reaction mixture advantageously doesnot exceed the above-specified temperature ranges. On completion ofaddition, the reaction mixture is allowed to continue to reactpreferably for from 5 minutes to 24 hours, in particular from 10 minutesto 6 hours, at a temperature below 30° C. The reaction conditions arepreferably selected in such a way that at least 85%, in particular atleast 90% and more preferably at least 95% of the polyisobutenylphenolare formed. The polyisobutene-substituted phenols obtained in this waypreferably consist of more than 85%, in particular more than 90% andmore preferably of more than 95%, of isomers whose polyisobutene radicalis in the para-position to the hydroxyl group of the phenol.

The above remarks on the alkylation of phenols V with polyisobutenesapply analogously for the alkylation with other polyolefins.

The phenols V or the Mannich adducts I preferably have a polydispersityin the range from 1.05 to 3.5, in particular from 1.1 to 2.5 and morepreferably from 1.1 to 1.9.

The setting of the desired polydispersity can be achieved by preciseselection of the starting materials, choice of the stoichiometry, choiceof the temperature and reaction time and also optionally of the workup,in particular by suitable purification techniques such as extraction anddistillation.

Suitable measures which, individually or in combination, favor theformation of adducts I having increased effectiveness and/or lowerpolydispersity are selected, for example, from

-   -   use of polyolefins of lower polydispersity to prepare the        phenols V,    -   use of polyolefins having very high proportions of terminal        double bonds,    -   use of the polyolefins in an amount that does not exceed the        amount of phenols in the alkylation thereof, optionally followed        by a subsequent removal of the unconverted phenol,    -   carrying out the alkylation at a very low temperature which        nevertheless ensures complete conversion, for example above        about +5° C. and below about +40° C.,    -   maintenance of a suitable stoichiometry; for example, an        aldehyde:amine:phenol V ratio of about 1:1:1 (to prepare        monoaminoalkylated Mannich adducts I) or about 2:2:1 (to prepare        bisaminoalkylated Mannich adducts I),    -   carrying out the Mannich(-like) reaction with an adduct of amine        and aldehyde or aldehyde equivalent in accordance with variant        B, in particular in accordance with the above-described        preferred embodiments,    -   extraction of the phenol V and/or of the Mannich base with polar        organic solvents, for example alcohols such as methanol,        ethanol, propanol, isopropanol, n-butanol, sec-butanol,        isobutanol and tert-butanol; ketones such as acetone, methyl        ethyl ketone, diethyl ketone and cyclohexanone; esters such as        methyl acetate, ethyl acetate, propyl acetate, isopropyl        acetate, methyl propionate and ethyl propionate; and nitriles        such as acetonitrile, propionitrile and butyronitrile.

Preference is given to using component B as a dispersant/detergentbecause the Mannich adducts can be more easily metered than the aminesof component A and because, in contrast to free amines, they constituteno odor nuisance. However, preference is given to using a mixture ofcomponents A and B, because such a mixture can satisfy differentrequirements in different direct-injection engine systems. The weightratio of component A to component B is preferably from 20:1 to 1:20,more preferably from 10:1 to 1:10 and in particular from 5:1 to 1:5.

In a preferred embodiment of both use variants, the Mannich adduct used,optionally in a mixture with component A, is of the formula I.1

where

-   -   R⁸ in use variant 1, is a polyisobutene radical having a        number-average molecular weight of preferably from 300 to 3000,        or, in use variant 2, is a poly(iso)butene radical having a        number-average molecular weight of preferably from 300 to 3000,    -   R⁹ is a C₁-C₆-alkyl group,    -   R¹⁰ is H or C₁-C₆-alkyl,    -   R¹ and R² are each independently C₆-C₃₀-alkyl,        CR¹¹R¹²)_(x)—NR⁴        _(Y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),        CR¹¹R¹²)_(x)—O        _(Y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (III) or        CR¹¹R¹²)_(x)—NR⁴        _(Y)(CR¹³R¹⁴)_(z)—OR⁵  (IV)        -   where R⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are each independently H            or C₁-C₆-alkyl,        -   R⁶ and R⁷ are each independently H, C₁-C₆-alkyl or            C₁-C₆-hydroxyalkyl,        -   x and z are each independently a number from 1 to 20,        -   y is a number from 0 to 10 and    -   m is 0 or 1.

R⁹ is preferably methyl or ethyl.

R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are preferably each H.

In a particularly preferred embodiment of both use variants, a Mannichadduct I.1 is used where m is 0, R¹⁰ is H and both R¹ and R² are eitherC₆-C₁₀-alkyl, in particular C₈-alkyl, especially 2-ethylhexyl, or agroup of the formula II where R¹¹, R¹², R¹³ and R¹⁴ are each H, y is 0,z is a number from 3 to 6 and R⁶ and R⁷ are each independently H,C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl. Preference is given to both R⁶ and R⁷each being methyl, ethyl, propyl, hydroxymethyl or hydroxyethyl. z isespecially 3 and R⁶ and R⁷ are especially each methyl. Equal preferenceis given to the use of a Mannich adduct I.1 where m is 0 or 1, R⁹ ismethyl, R¹⁰ is H, R¹ is H and R² is a group of the formula II where R¹¹,R¹², R¹³ and R¹⁴ are each H, y is 0, z is a number from 3 to 6 and R⁶and R⁷ are each independently H, C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl. BothR⁶ and R⁷ are preferably each methyl, ethyl, propyl, hydroxymethyl orhydroxyethyl. z is especially 3 and R⁶ and R⁷ are preferably eachmethyl, i.e. NR¹R² is especially N[(CH₂)₃N(CH₃)₂]₂.

Component A, component B or mixtures thereof can be used as fuel orlubricant concentrates. The individual components A or B or theirmixture is present in an amount of preferably from 0.1 to 80% by weight,more preferably from 10 to 70% by weight and in particular from 30 to60% by weight. Component A, component B or their mixture are present ina diluent. Suitable diluents are, for example, aliphatic and aromatichydrocarbons, such as Solvent Naphtha. Preference is given to usinglow-sulfur hydrocarbons as diluents.

The present invention further provides a process for reducing depositsin direct-injection gasoline engines by providing a fuel which comprisesa component A or a component B, both of which are as defined above, or amixture thereof. The remarks made with regard to the preferredembodiments of components A and B apply here correspondingly.

In a preferred embodiment of the process, the engine is operated forpreferably more than 80% of the operating time at a lambda value of atleast 0.9 up to and including 9, more preferably from 0.95 to 8 and inparticular from 0.97 to 6.

The present invention further provides fuel and lubricant compositionsfor direct-injection gasoline engines, comprising a majority of ahydrocarbon fuel or of a lubricant, and a detergent-active amount ofcomponent B, as defined in use variant 2. The remarks made there withregard to the preferred embodiments of component B applycorrespondingly. The fuel and lubricant compositions according to theinvention preferably comprise component B in an amount of from 5 to 5000ppm, more preferably from 10 to 1000 ppm and in particular from 20 to500 ppm.

Useful fuels include all commercial gasoline fuels which are suitablefor operating direct-injection gasoline engines.

In a preferred embodiment, the fuel and lubricant compositions compriseat least one Mannich adduct of the formula I.1

-   -   where    -   R⁸ is a poly(iso)butene radical having a number-average        molecular weight of from 300 to 3000,    -   R⁹ is a C₁-C₆-alkyl group,    -   R¹⁰ is H or C₁-C₆-alkyl,    -   R¹ and R² are each independently        -   C₆-C₂₀-alkyl, C₆-C₂₀-cycloalkyl,            CR¹¹R¹²)_(x)—NR⁴            _(Y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),            CR¹¹R¹²)_(x)—O            _(Y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (III) or            CR¹¹R¹²)_(x)—NR⁴            _(Y)(CR¹³R¹⁴)_(z)—OR⁵  (IV)        -   where R⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are each independently H            or C₁-C₆-alkyl,        -   R⁶ and R⁷ are each independently H, C₁-C₆-alkyl or            C₁-C₆-hydroxyalkyl,        -   x and z are each independently a number from 1 to 20,        -   y is a number from 0 to 10 and    -   m is 0 or 1.

With regard to the preferred definitions of the variables R¹ to R¹⁴ andalso of x, z, y and m, the remarks made above apply.

The present application further provides an additive concentratecomprising a component B, at least one diluent and also optionally atleast one further additive. Component B is defined as described in usevariant 2. The remarks made there with regard to the preferredembodiments of component B apply correspondingly. Component B is presentin an amount of preferably from 0.1 to 80% by weight, more preferablyfrom 10 to 70% by weight and in particular from 30 to 60% by weight,based on the weight of the concentrate. Suitable diluents are, forexample, aliphatic and aromatic hydrocarbons, such as Solvent Naphtha.Preference is given to using low-sulfur hydrocarbons as diluents.

In addition to component B, the fuel and lubricant compositionsaccording to the invention and also the fuel and lubricant concentratesoptionally comprise further customary fuel and lubricant additives,preferably the additives described hereinbelow.

Examples of additives which are used in the fuels and lubricantsaccording to the invention or in the concentrates are further additivesother than component B which have detergent action or have valve seatwear-inhibiting action, and each have at least one hydrophobichydrocarbon radical having a number-average molecular weight (M_(N)) offrom 85 to 20000 and at least one polar moiety selected from

-   (a) mono- or polyamino groups having up to 6 nitrogen atoms, at    least one nitrogen atom having basic properties,-   (b) hydroxyl groups in combination with mono- or polyamino groups,    at least one nitrogen atom having basic properties,-   (c) carboxyl groups or their alkali metal or alkaline earth metal    salts,-   (d) polyoxy-C₂— to —C₄-alkylene moieties which are terminated by    hydroxyl groups, mono- or polyamino groups, at least one nitrogen    atom having basic properties, or by carbamate groups,-   (e) carboxylic ester groups,-   (f) moieties derived from succinic anhydride and having hydroxyl    and/or amino and/or amido and/or imido groups and-   (g) moieties obtained by conventional Mannich reaction of phenolic    hydroxyl groups with aldehydes and mono- or polyamines.

Examples of above additive components having detergent action include:

Additives containing mono- or polyamino groups (a) are preferablypolyalkenemono- or polyalkenepolyamines based on polypropene or onhighly reactive (i.e. having predominantly terminal double bonds,usually in the β- and γ-position) or conventional (i.e. havingpredominantly internal double bonds) polybutene or polyisobutene havingan M_(N) of from 600 to 5000, none of which have been obtained byabove-described processes for preparing polyisobutenylphenols. Suchadditives based on reactive polyisobutene, which can be prepared fromthe polyisobutene (which may contain up to 20% by weight of n-buteneunits) by hydroformylation and reductive amination with ammonia,monoamines or polyamines, such as dimethylaminopropylamine,ethylenediamine, diethylenetriamine, triethylenetetramine ortetraethylenepentamine, are disclosed in particular in EP-A 244 616.When polybutene or polyisobutene having predominantly internal doublebonds (usually in the β- and γ-position) are used as starting materialsin the preparation of the additives, a possible preparative route is bychlorination and subsequent amination or by oxidation of the double bondwith air or ozone to give the carbonyl or carboxyl compound andsubsequent amination under reductive (hydrogenating) conditions. Theamines used here for the amination may be the same as those used abovefor the reductive amination of the hydroformylated reactivepolyisobutene. Corresponding additives based on polypropene aredescribed in particular in WO-A 94/24231.

Further preferred additives containing monoamino groups (a) are thehydrogenation products of the reaction products of polyisobutenes havingan average degree of polymerization P of from 5 to 100 with nitrogenoxides or mixtures of nitrogen oxides and oxygen, as described inparticular in WO-A 97/03946.

Further preferred additives containing monoamino groups (a) are thecompounds obtainable from polyisobutene epoxides by reaction with aminesand subsequent dehydration and reduction of the amino alcohols, asdescribed in particular in DE-A 196 20 262.

Additives containing hydroxyl groups in combination with mono- orpolyamino groups (b) are in particular reaction products ofpolyisobutene epoxides, obtainable from polyisobutene having preferablypredominantly terminal double bonds and an M_(N) of from 600 to 5000,with ammonia or mono- or polyamines, as described in particular in EP-A476 485.

Additives containing carboxyl groups or their alkali metal or alkalineearth metal salts (c) are preferably copolymers of C₂-C₄₀-olefins withmaleic anhydride which have a total molar mass of from 500 to 20000 andsome or all of whose carboxyl groups have been converted to the alkalimetal or alkaline earth metal salts and any remainder of the carboxylgroups has been reacted with alcohols or amines. Such additives aredisclosed in particular by EP-A 307 815. Such additives can, asdescribed in WO-A 87/01126, advantageously be used in combination withcustomary fuel detergents such as poly(iso)butenamines orpolyetheramines.

Additives containing polyoxy-C₂- to C₄-alkylene moieties (d) arepreferably polyethers or polyetheramines which are obtainable byreaction of C₂- to C₆₀-alkanols, C₆- to C₃₀-alkanediols, mono- ordi-C₂-C₃₀-alkylamines, C₁-C₃₀-alkylcyclohexanols or C₁-C₃₀-alkylphenolswith from 1 to 30 mol of ethylene oxide and/or propylene oxide and/orbutylene oxide per hydroxyl group or amino group and, in the case of thepolyetheramines, by subsequent reductive amination with ammonia,monoamines or polyamines. Such products are described in particular inEP-A 310 875, EP-A 356 725, EP-A 700 985 and U.S. Pat. No. 4,877,416. Inthe case of polyethers, such products also have carrier oil properties.Typical examples of these are tridecanol butoxylates, isotridecanolbutoxylates, isononylphenol butoxylates and polyisobutenol butoxylatesand propoxylates and also the corresponding reaction products withammonia.

Additives containing carboxylic ester groups (e) are preferably estersof mono-, di- or tricarboxylic acids with long-chain alkanols orpolyols, in particular those having a minimum viscosity of 2 mm² at 100°C., as described in particular in DE-A 38 38 918. The mono-, di- ortricarboxylic acids used may be aliphatic or aromatic acids, andparticularly suitable ester alcohols or ester polyols are long-chainrepresentatives having, for example, from 6 to 24 carbon atoms. Typicalrepresentatives of the esters are adipates, phthalates, isophthalates,terephthalates and trimellitates of isooctanol, of isononanol, ofisodecanol and of isotridecanol. Such products also have carrier oilproperties.

Additives containing moieties derived from succinic anhydride and havinghydroxyl and/or amino and/or amido and/or imido groups (f) arepreferably corresponding derivatives of polyisobutenyl succinicanhydride which are obtainable by reacting conventional or highlyreactive polyisobutene having an M_(N) of from 300 to 5000 with maleicanhydride by a thermal route or via the chlorinated polyisobutene.Particular interest attaches to derivatives with aliphatic polyaminessuch as ethylenediamine, diethylenetriamine, triethylenetetramine ortetraethylenepentamine. Such gasoline fuel additives are described inparticular in U.S. Pat. No. 4,849,572.

Additives containing moieties produced by conventional Mannich reactionof phenolic hydroxyl groups with aldehydes and mono- or polyamines (g)correspond to the above-described Mannich adducts I where the sum of themolecular weight of all NR¹R² radicals is less than 120 g/mol.

For a more precise definition of the gasoline fuel additives detailedindividually, reference is explicitly made here to the disclosures ofthe abovementioned prior art documents.

Useful solvents or diluents (when providing additive packages andconcentrates) include the diluents mentioned above in the case of theconcentrates according to the invention, for example aliphatic andaromatic hydrocarbons such as Solvent Naphtha.

Examples of further customary additive components which can be combinedwith the additives according to the invention are corrosion inhibitors,for example based on ammonium salts of organic carboxylic acids, saidsalts tending to form films, or on heterocyclic aromatics, antioxidantsor stabilizers, for example based on amines such as p-phenylenediamine,dicyclohexylamine or derivatives thereof or on phenols such as2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionicacid, demulsifiers, antistats, metallocenes such as ferrocene ormethylcyclopentadienylmanganese tricarbonyl, lubricity additives such ascertain fatty acids, alkyl succinic esters, bis(hydroxyalkyl) fattyamines, hydroxyacetamides or castor oil and also markers. Amines arealso optionally added to lower the pH of the fuel.

Further customary components also include carrier oils. These include,for example, mineral carrier oils (base oils), in particular those ofthe “Solvent Neutral (SN) 500 to 2000” viscosity class, syntheticcarrier oils based on olefin polymers having an M_(N) of from 400 to1800, in particular based on polybutene or polyisobutene (hydrogenatedor unhydrogenated), on poly-alpha-olefins or poly-internal olefins andalso synthetic carrier oils based on alkoxylated long-chain alcohols orphenols. Likewise suitable as further additives are polyalkenealcohol-polyetheramines, as described, for example, in DE-199 16 512.2.

The present invention further provides a Mannich adduct of the formulaI.1

-   -   where    -   R⁸ is a poly(iso)butene radical having a number-average        molecular weight of from 300 to 3000,    -   R⁹ is a C₁-C₆-alkyl group,    -   R¹⁰ is H or C₁-C₈-alkyl,    -   R¹ and R² are each independently        -   C₆-C₂₀-alkyl, C₈-C₂₀-cycloalkyl,            CR¹¹R¹²)_(x)—NR⁴            _(Y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),            CR¹¹R¹²)_(x)—O            _(Y)(CR¹³R¹⁴)_(z)—NR⁶R⁷  (III) or            CR¹¹R¹²)_(x)—NR⁴            _(Y)(CR¹³R¹⁴)_(z)—OR⁵  (IV)        -   where R⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are each independently H            or C₁-C₆-alkyl,        -   R⁶ and R⁷ are each independently H, C₁-C₆-alkyl or            C₁-C₆-hydroxyalkyl,        -   x and z are each independently a number from 1 to 20,        -   y is a number from 0 to 5 and    -   m is 0 or 1.

With regard to the preferred R⁸ radicals, reference is made to the aboveremarks.

R⁹ is preferably methyl or ethyl, more preferably methyl.

m is 0 or 1 and especially 0.

With regard to the preferred R¹ and R² radicals, the above remarksapply.

In a particularly preferred embodiment, m is 0, R¹⁰ is H and both R¹ andR² are each either C₈-C₁₀-alkyl, in particular C₈-alkyl, especially2-ethylhexyl, or a group of the formula II where R¹¹, R¹², R¹³ and R¹⁴are each H, y is 0, z is a number from 3 to 6 and R⁶ and R⁷ are eachindependently H, C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl. R⁶ and R⁷ arepreferably both each methyl, ethyl, propyl, hydroxymethyl orhydroxyethyl. z is especially 3 and R⁶ and R⁷ are especially eachmethyl. Equal preference is given to the use of a Mannich adduct I.1where m is 0 or 1, R⁹ is methyl, R¹⁰ is H, R¹ is H and R² is a group ofthe formula II where R¹¹, R¹², R¹³ and R¹⁴ are each H, y is 0, z is anumber from 3 to 6 and R⁶ and R⁷ are each independently H, C₁-C₆-alkylor C₁-C₆-hydroxyalkyl. Both R⁶ and R⁷ are preferably each methyl, ethyl,propyl, hydroxymethyl or hydroxyethyl. z is especially 3 and R⁶ and R⁷are preferably each methyl, i.e. both R¹ and R² are eachN,N-dimethylaminopropyl.

In a likewise particularly preferred embodiment, the R¹ and R² radicalsare each a C₆-C₁₀-alkyl radical, in particular a C₈-alkyl radical,especially 2-ethylhexyl.

The use according to the invention of component A or component B ormixtures thereof leads to a distinct reduction in the formation ofdeposits at the injection nozzles of direct-injection gasoline engines.

The nonlimiting examples which follow illustrate the invention.

EXAMPLES I. Preparation of 4-polyisobutenylphenol and of2-methyl-4-polyisobutenylphenol I.1 Preparation of4-polyisobutenylphenol

The preparation was effected starting from phenol and Glissopal 1000 bya process described in DE-A 19948111.

In a 4 l four-neck flask, 203.9 g of phenol were melted under nitrogenat from 40 to 45° C. 95.5 g of BF₃-diethyl ether adduct were addeddropwise and the mixture was cooled to from 20 to 25° C. 998 g ofpolyisobutene having an M_(N) of 1000 and a dimethylvinylidene contentof 85%, dissolved in 1800 ml of hexane, were added dropwise at from 20to 25° C. within 3 hours. Stirring was continued overnight.Subsequently, the reaction was ended by adding 500 ml of 25% ammoniasolution. The organic phase was removed and subsequently washed 7 timeswith 500 ml of water and dried over Na₂SO₄, and the solvent was removedunder reduced pressure: 1060 g of oil (polyisobutenylphenol).

NMR: 7.2 ppm (doublet, 2H), 6.7 ppm (doublet, 2H), 4.8 ppm (singlet,broad 1H), 1.75 ppm (singlet, 2H), 1.5-0.5 ppm (singlet, 165H).

This corresponds to an M_(N) of the alkyl radical of 1150. Within therange from 7.1 to 6.75 there are small signals which suggest that, inaddition to the main product (p-polyisobutenylphenol), from 5 to 10% of2,4-substituted phenol have formed which is in agreement with the lowmolecular weight increase determined.

I.2 Preparation of 2-methyl-4-polyisobutenylphenol

The preparation was effected starting from cresol and Glissopal 1000 bya process described in DE-A 19948111.

In a 4 l four-neck flask, 234.3 g of cresol were melted under nitrogenat from 40 to 45° C. 95.5 g of BF₃-diethyl ether adduct were addeddropwise and the mixture was cooled to from 20 to 25° C. 998 g ofpolyisobutene having an M_(N) of 1000 and a dimethylvinylidene contentof 85%, dissolved in 1800 ml of hexane, were added dropwise at from 20to 25° C. within 3 hours. Stirring was continued overnight.Subsequently, the reaction was ended by adding 500 ml of 25% ammoniasolution. The organic phase was removed and subsequently washed 7 timeswith 500 ml of water and dried over Na₂SO₄, and the solvent was removedunder reduced pressure. 2-Methyl-4-polyisobutenylphenol was obtained inthe form of an oil.

II. Conversion of Polyisobutenylphenols to Mannich Adducts I II.1Reaction of the polyisobutenylphenol from I.1 with paraformaldehyde andN,N-bis[3-(N′,N′-dimethylamino)propyl]amine

A 1 l flask equipped with a water separator was initially charged with219.8 g of 4-polyisobutenylphenol from I.1 in 1000 ml of xylene. 15.1 gof paraformaldehyde were added and the mixture was heated to 90° C. for1 h. Subsequently, 93.9 g of N,N-bis[3-(N′,N′-dimethylamino)propyl]aminewere added rapidly, whereupon 8 ml of aqueous phase separated. Thesolution was concentrated on a rotary evaporator at 145° C. and 5 mbar.A product mixture of 10% of monoaminoalkylated and 90% ofbisaminoalkylated polyisobutenylphenol were obtained as a light-coloredoil in a yield of 278.4 g. The mono- and bisaminomethylated productswere identified by means of the shifting of the benzylic proton(aromatic ring-CH ₂—NR⁵R⁶) in the ¹H NMR spectrum.

II.2 Reaction of the polyisobutenylphenol from I.1 with paraformaldehydeand N,N-di(2-ethylhexyl)amine

In a similar manner to II.1, the polyisobutenylphenol from I.1 wasreacted with paraformaldehyde and N,N-di(2-ethylhexyl)amine in a molarratio of 1:1.2:1.2. The reaction resulted in a product mixture of 90% ofmonoaminoalkylated and 4% of bisaminoalkylated polyisobutenylphenol.

II.3 Reaction of the polyisobutenylphenol from I.1 with paraformaldehydeand N,N-di(2-ethylhexyl)amine

In a similar manner to II.1, the polyisobutenylphenol from I.1 wasreacted with paraformaldehyde and N,N-di(2-ethylhexyl)amine in a molarratio of 1:2.4:2.4. The reaction resulted in a product mixture of 20% ofmonoaminoalkylated and 80% of bisaminoalkylated polyisobutenylphenol.

II.4 Reaction of the polyisobutenylcresol from I.2 with paraformaldehydeand N′,N′-3-(dimethylamino)propylamine

In a similar manner to II.1, N′,N′-3-(dimethylamino)propylamine wasreacted with the polyisobutenylcresol from I.2 in a cresol to amine toaldehyde ratio of 1:1:1. The monoaminomethylated cresol was obtained ina yield of 80%. No bisaminomethylated cresol was obtained.

III. Engine Tests Test Engine

The test engine used was a modern direct-injection gasoline engine whosecylinder geometry is configured in a such a way that uniform fueldistribution takes place. The experiments were carried out in the leanrange.

Type: Four-cylinder, four-stroke, 2.0 l Capacity: 1998 cm³ Sparkplugs/cylinder: 1 Valves/cylinder: 4 Bore: 86 mm Stroke: 86 mm Injectionsystem: Common Rail high pressure DI Injection pressure: approx. 100 barTemperature of the cooling liquid: 90° C. Oil temperature: 94° C. Testcycle: M 102 E (CEC F-05-A-93), 100 h Fuel: sulfur-free Superplus to DINEN 228

The fuel was admixed with 5 different additive packages and subjected tothe abovementioned test cycle. Subsequently, the appearance in theinterior of the injection nozzle was evaluated.

Additive packages: In addition to the additives specified, the solventcontained in all additive packages was a mixture of xylene andC₁₁-C₁₄-paraffins.

Additive package 1 39% by weight of Mannich adduct a* (comparative) 17%by weight of polypropoxylate-fatty alcohol ether 44% by weight ofsolvent Additive package 2 39% by weight of Mannich adduct b**(comparative) 17% by weight of polypropoxylate-fatty alcohol ether 44%by weight of solvent Additive package 3 39% by weight of Mannich adductc*** 17% by weight of polypropoxylate-fatty alcohol ether 44% by weightof solvent Additive package 4  9% by weight of tridecylamine 36% byweight of Mannich adduct a* 15% by weight of polypropoxylate-fattyalcohol ether 40% by weight of solvent Additive package 5  9% by weightof ethylhexylamine 36% by weight of Mannich adduct a* 15% by weight ofpolypropoxylate-fatty alcohol ether 40% by weight of solvent *Mannichadduct a: Mannich adduct of the formula I where m = 0 n = 1 R⁸ = radicalderived from reactive polyisobutene R¹⁰ = H R¹, R² = methyl The Mannichadduct a is obtainable by reaction of the polyisobutenylphenol fromexample I.1 with formaldehyde and dimethylamine in approximatelyequimolar amounts. **Mannich adduct b: Mannich adduct of the formula Iwhere m = 0 n = 1 R⁸ = radical derived from low-reactivity polyisobuteneR¹⁰ = H R¹ = H R² = 3-N,N-dimethylaminopropyl The Mannich adduct b isobtainable by reaction according to WO 01/42399, p. 16. ***Mannichadduct c: Mannich adduct of the formula I where m = 0 n = 2 R⁸ = radicalderived from reactive polyisobutene R¹⁰ = H R¹, R² =3-N,N-dimethylaminopropyl

The Mannich adduct c is obtainable by reaction according to II.1

Additive Appearance in the interior package No. Dosage [mg/kg] of theinjection nozzles — — heavy deposits 1 500 heavy deposits 2 500 heavydeposits 3 500 clean 4 550 clean 5 550 slight deposits

As the engine test shows, the components A and B used in accordance withthe invention in the additive packages 3 to 5, unlike the prior artadditives, substantially prevent the formation of deposits in the enginechamber of direct-injection gasoline engines.

We claim:
 1. A process for reducing deposits in a direct-injectiongasoline engine, comprising: directly injecting a fuel into a combustionchamber of the direct injection gasoline engine through a nozzledisposed in the combustion chamber; wherein the fuel comprises acomponent B comprising at least one Mannich adduct of the formula I

where R¹ and R² are each independently H, C₁-C₂₀-alkyl orC₃-C₂₀-cycloalkyl, and two alkyl radicals together with the nitrogenatom to which they are bonded may form a ring and the alkyl and thecycloalkyl radicals may be interrupted by one or more groups selectedfrom O and NR⁴ and/or may be substituted by one or more OR⁵ or NR⁶R⁷groups, where R⁴, R⁵, R⁶ and R⁷ are each independently H, C₁-C₂₀-alkylor C₃-C₂₀-cycloalkyl, R⁸ is a polyisobutene radical which is derivedfrom reactive a polyisobutene polymer having at least 50 mol %, based onthe total number of polyisobutene macromolecules, of terminal doublebonds, R⁹ is a C₁-C₆-alkyl group, R¹⁰ is H or C₁-C₆-alkyl, m is a numberfrom 0 to (4-n) and n is a number from 1 to 3, with the proviso that thesum of the molecular weights of the radicals NR¹R² is from 120 to 1,000g/mol.
 2. The process as claimed in claim 1, wherein the sum of themolecular weights of the radicals NR¹R² in component B is from 180 to600 g/mol.
 3. The process as claimed in claim 1, wherein the radicals R¹and R² in component B are each independently H, C₆-C₂₀-alkyl,C₆-C₂₀-cycloalkyl,

CR¹¹R¹²)_(x)—NR⁴

_(y)

CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),

CR¹¹R¹²)_(x)—O

_(y)

CR¹³R¹⁴)_(z)—NR⁶R⁷  (III) or

CR¹¹R¹²)_(x)—NR⁴

_(y)

CR¹³R¹⁴)_(z)—OR⁵  (IV) where R⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are eachindependently H or C₁-C₆-alkyl, R⁶ and R⁷ are each independently H,C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl, x and z are each independently anumber from 1 to 20 and y is a number from 0 to
 10. 4. The process asclaimed in claim 1, wherein R⁸ is a polyisobutene radical which isderived from reactive polyisobutenes.
 5. The process as claimed in claim1, wherein R⁸ in component B is in the p-position to the OH group. 6.The process as claimed in claim 1, wherein component B is employed inthe form of a fuel or lubricant concentrate comprising component B in anamount of from 0.1 to 80% by weight.
 7. A process as claimed in claim 1,in which the direct-injection gasoline engine is operated at a lambdavalue of from 0.9 to
 9. 8. A process as claimed in claim 1, whereincomponent B comprises at least one Mannich adduct of the formula I.1

wherein R⁸ is a polyisobutene radical having a number-average molecularweight of from 300 to 3000, R¹ and R² are each independentlyC₆-C₂₀-alkyl, C₆-C₂₀-cycloalkyl,

CR¹¹R¹²)_(x)—NR⁴

_(y)

CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),

CR¹¹R¹²)_(x)—O

_(y)

CR¹³R¹⁴)_(z)—NR⁶R⁷  (III) or

CR¹¹R¹²)_(x)—NR⁴

_(y)

CR¹³R¹⁴)_(z)—OR⁵  (IV), R⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are eachindependently H or C₁-C₆-alkyl, R⁶ and R⁷ are each independently H,C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl, R⁹ is a C₁-C₆-alkyl group, x and zare each independently a number from 1 to 20 and y is a number from 0 to10; and m is 0 or
 1. 9. The process as claimed in claim 1, wherein thefuel is injected in the combustion chamber under lean conditions.
 10. Aprocess for reducing deposits in a direct-injection gasoline engine,comprising: directly injecting a fuel into a combustion chamber of thedirect injection gasoline engine through a nozzle disposed in thecombustion chamber; wherein the fuel comprises a component B comprisingat least one Mannich adduct of the formula I

where R¹ and R² are each independently H, C₁-C₂₀-alkyl orC₃-C₂₀-cycloalkyl, and two alkyl radicals together with the nitrogenatom to which they are bonded may form a ring and the alkyl and thecycloalkyl radicals may be interrupted by one or more groups selectedfrom O and NR⁴ and/or may be substituted by one or more OR⁵ or NR⁶R⁷groups, where R⁴, R⁵, R⁶ and R⁷ are each independently H, C₁-C₂₀-alkylor C₃-C₂₀-cycloalkyl, R⁸ is a polyisobutene radical which is derivedfrom a reactive polyisobutene polymer having at least 50 mol %, based onthe total number of polyisobutene macromolecules, of terminal doublebonds, R⁹ is a C₁-C₆-alkyl group, R¹⁰ is H or C₁-C₆-alkyl, m is a numberfrom 0 to (4-n), and n is 2, with the proviso that the sum of themolecular weights of the radicals NR¹R² is from 120 to 1,000 g/mol. 11.The process as claimed in claim 10, wherein the sum of the molecularweights of the radicals NR¹R² in component B is from 180 to 600 g/mol.12. The process as claimed in claim 10, wherein the radicals R¹ and R²in component B are each independently H, C₆-C₂₀-alkyl,C₆-C₂₀-cycloalkyl,

CR¹¹R¹²)_(x)—NR⁴

_(y)

CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),

CR¹¹R¹²)_(x)—O

_(y)

CR¹³R¹⁴)_(z)—NR⁶R⁷  (III) or

CR¹¹R¹²)_(x)—NR⁴

_(y)

CR¹³R¹⁴)_(z)—OR⁵  (IV) where R⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are eachindependently H or C₁-C₆-alkyl, R⁶ and R⁷ are each independently H,C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl, x and z are each independently anumber from 1 to 20 and y is a number from 0 to
 10. 13. The process asclaimed in claim 10, wherein R⁸ in component B is in the p-position tothe OH group.
 14. The process as claimed in claim 10, wherein componentB is employed in the form of a fuel or lubricant concentrate comprisingcomponent B in an amount of from 0.1 to 80% by weight.
 15. A process asclaimed in claim 10, in which the direct-injection gasoline engine isoperated at a lambda value of from 0.9 to
 9. 16. A process as claimed inclaim 10, wherein component B comprises at least one Mannich adduct ofthe formula I.1

wherein R⁸ is a polyisobutene radical having a number-average molecularweight of from 300 to 3000, R¹ and R² are each independentlyC₆-C₂₀-alkyl, C₆-C₂₀-cycloalkyl,

CR¹¹R¹²)_(x)—NR⁴

_(y)

CR¹³R¹⁴)_(z)—NR⁶R⁷  (II),

CR¹¹R¹²)_(x)—O

_(y)

CR¹³R¹⁴)_(z)—NR⁶R⁷  (III) or

CR¹¹R¹²)_(x)—NR⁴

_(y)

CR¹³R¹⁴)_(z)—OR⁵  (IV), R⁴, R⁵, R¹¹, R¹², R¹³ and R¹⁴ are eachindependently H or C₁-C₆-alkyl, R⁶ and R⁷ are each independently H,C₁-C₆-alkyl or C₁-C₆-hydroxyalkyl, R⁹ is a C₁-C₆-alkyl group, x and zare each independently a number from 1 to 20, y is a number from 0 to10, and m is 0 or
 1. 17. A process as claimed in claim 16, wherein R⁸ isa polyisobutene radical which is derived from reactive polyisobuteneshaving at least 50 mol %, based on the total number of polyisobutenemacromolecules of terminal double bonds.
 18. The process as claimed inclaim 10, wherein the fuel is injected in the combustion chamber underlean conditions.
 19. The process as claimed in claim 10, wherein R⁸ is apolyisobutene radical having at least 80 mol % of terminal double bonds.20. The process as claimed in claim 10, wherein the terminal doublebonds of the polyisobutene radical are vinyl double bonds [—CH═C(CH₃)₂].21. The process as claimed in claim 10, wherein the terminal doublebonds of the polyisobutene radical are vinylidene double bonds[—CH₂—C(═CH₂)—CH₃].
 22. The process as claimed in claim 1, wherein R⁸ isa polyisobutene radical having at least 80 mol % of terminal doublebonds.
 23. The process as claimed in claim 1, wherein the terminaldouble bonds of the polyisobutene radical are vinyl double bonds[—CH═C(CH₃)₂].
 24. The process as claimed in claim 1, wherein theterminal double bonds of the polyisobutene radical are vinylidene doublebonds [—CH₂—C(═CH₂)—CH₃].
 25. The process as claimed in claim 10,wherein where R¹ and R² are each independently H, C₁-C₂₀-alkyl orC₃-C₂₀-cycloalkyl, and two alkyl radicals together with the nitrogenatom to which they are bonded may form a ring, where R⁴, R⁵, R⁶ and R⁷are each independently H, C₁-C₂₀-alkyl or C₃-C₂₀-cycloalkyl, R⁸ is apolyisobutene radical which is derived from a reactive polyisobutenepolymer having at least 50 mol %, based on the total number ofpolyisobutene macromolecules, of terminal double bonds, R⁹ is aC₁-C₆-alkyl group, R¹⁰ is H or C₁-C₆-alkyl.
 26. The process as claimedin claim 1, wherein where R¹ and R² are each independently H,C₁-C₂₀-alkyl or C₃-C₂₀-cycloalkyl, and two alkyl radicals together withthe nitrogen atom to which they are bonded may form a ring, where R⁴,R⁵, R⁶ and R⁷ are each independently H, C₁-C₂₀-alkyl orC₃-C₂₀-cycloalkyl, R⁸ is a polyisobutene radical which is derived from areactive polyisobutene polymer having at least 50 mol %, based on thetotal number of polyisobutene macromolecules, of terminal double bonds,R⁹ is a C₁-C₆-alkyl group, R¹⁰ is H or C₁-C₆-alkyl.